Method of preparing a stable, low pH phenolic resin

ABSTRACT

A phenol-formaldehyde resole resin for use as a binder for glass fibers is acidified to a pH of 3 or less after base-catalyzed resinification. An increase in actual solids is observed compared with neutralized resin. Phenol-formaldehyde-urea-ammonia resins are surprisingly stable at pH 3 with desirable cure profiles.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to the manufacture of fiberglass insulation materials, and more particularly to the preparation of phenolic resin for glass fibers.

[0003] 2. Brief Description of the Prior Art

[0004] Aqueous dispersions of phenol-formaldehyde resole resins are frequently used in the manufacture of glass fiber insulation materials, such as insulative batts for walls, in roofs and ceilings, insulative coverings for pipes, and the like. Typically, after glass fiber has been formed, the still hot fiber is sprayed with aqueous binder dispersion in a forming chamber or hood, with the fibers being collected on a conveyer belt in the form of a wool-like mass associated with the binder. In some cases, a glass fiber web is sprayed with the aqueous dispersion. Both resole and urea-modified resole resins have been employed for this purpose, the urea contributing to the “punking” resistance of the binder (i.e., resistance to exothermic decomposition at elevated temperatures), and reducing volatiles liberated when the resin is cured at elevated temperature.

[0005] An excess of formaldehyde over phenol is typically used so as to minimize the free phenol in the reaction product. Subsequently, other components (for example, urea) may be included to scavenge free formaldehyde.

[0006] Frequently, in the manufacture of glass fiber insulation materials, the aqueous resole resin is prepared in advance of the preparation of the binder, or is supplied by a resin manufacturer and stored until shortly before use. The resole is typically prepared by reaction of phenol and formaldehyde under basic conditions, the resulting reaction mixture being neutralized to a slightly basic pH by addition of a strong acid, to provide a water-dilutable resole. Subsequently, the binder is prepared by adding to the resole resin an acid catalyst for curing the resin, water to dilute the dispersion, and optionally other components, such as a silane glass-adhesion promoter, an oil emulsion lubricant, and urea to reduce volatile materials liberated during curing.

[0007] It is desirable to obtain the highest possible level of solids during preparation of the resole resin. High solids correlate with reduced volatile liberation and enhanced efficiency.

[0008] The resole resin can be prepared by any of a variety of specific processes, such as disclosed in U.S. Pat. No. 5,300,562, hereby incorporated by reference. Often, a single stage process is employed. Phenol and formaldehyde are mixed with a strongly basic catalyst, such as an alkali metal base, and the mixture is maintained at an elevated temperature until the desired degree of reaction has occurred, after which time the reaction mixture is cooled and neutralized by addition of a suitable acid. Alternatively, a multiple step process can be employed such one involving an initial reaction step under acid conditions and a subsequent reaction step under basic conditions, followed by neutralization.

[0009] U.S. Pat. No. 5,362,842 discloses a two-step process for making a urea-formaldehyde resin composition including an initial step under basic conditions and a second step under acidic conditions, during which the pH is maintained in the range from 4.9 to 5.2.

[0010] U.S. Pat. Nos. 5,358,748 and 5,505,998 disclose an acidic glass fiber binding composition. A strong aqueous soluble acid is employed in preparing the binder composition in order to reduce the level of alkylamine otherwise produced during cure. Alklyamines are disclosed to be undesirable odiferous materials produced by degradation of urea (the formaldehyde scavenger) during cure. A strong acid, that is, an acid with a pK_(a) value of 4 or less, is added to the binder composition to lower the pH to a value between 4.5 and 6.5, preferably between 4.5 and 6. Suitable acids include sulfamic acid, oxalic acid and sulfuric acid. The binder includes a phenol formaldehyde resin, preferably having a low free formaldehyde content and a low free phenol content. According to this patent, most commercially available phenol formaldehyde resins have an alkaline pH range, such as between 9 and 9.6, and this makes the addition of the strong acid to provide a pH between 4.5 and 6.5 a quite different thing.

[0011] According to U.S. Pat. No. 5,538,761, phenol-formaldehyde condensates prepared under acid conditions or with low levels of formaldehyde under basic conditions are generally not water soluble, as significant quantities of insoluble dihydroxydiphenylmethanes are produced.

[0012] U.S. Pat. No. 5,538,761 discloses a process for preparing binder-treated fiberglass exhibiting lower formaldehyde and ammonia emissions by use of an acidifying hydrolyzable salt, a mineral acid, or partial ester of carboxylic acid to lower the instantaneous pH of the urea-extended pre-react binder solution to less than 5.5, and preferably in the range 3.0 to 5.0, and more preferably in the range 4.0 to 5.0. The process also includes coating fiberglass with the acidified solution, and curing the binder. The “pre-react” is a binder solution comprising phenol-formaldehyde resole resin to which urea has been added and permitted to react with the free formaldehyde.

[0013] U.S. Pat. No. 5,864,003 discloses a thermosetting resin composition containing a mixture of a phenol-formaldehyde resole resin and a latent curing agent. The latent curing agent acts synergistically with a strong acid catalyst of the type conventionally used to cure phenol resole resins. Such strong acid catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid and organic acids such as sulfamic acid, tricholoracetic acid, and aromatic di- and polysulfonic acids, such as phenyl sulfonic and other organosulfonic acids. The U.S. Pat. No. 5,864,003 patent notes that the resole resin can be neutralized after alkaline reaction of the phenol and formaldehyde using a conventional acid neutralizing agent such as methane sulfonic acid, hydrochloric acid, phosphoric acid, or sulfuric acid. Neutralization is accomplished by adding a sufficient amount of acid to establish a pH of between 6.5 and 7.5 in the aqueous resin, although a pH as low as 4.0 may result in stable resin systems.

[0014] Given the large volume of resinous binder compositions required in the production of fiberglass insulation and for other uses, and the need to minimize offensive emissions of formaldehyde and other compounds during manufacture, there is a continuing need for phenol-formaldehyde resin compositions for use in binders which exhibit low emissions during cure, and that have high solids.

SUMMARY OF THE INVENTION

[0015] The present invention provides an improved method or process for preparing a phenolic resin for use as a binder for glass fibers and giving higher solids than prior art processes. Higher solid compositions are very desirable from an emission-reduction perspective. This process provides more efficient resin compositions by increasing the solids level of the resin composition, and reduced emissions during cure, while maintaining good storage stability, as determined by the water dilutability of the resin composition, and exhibiting good curing characteristics. The process can be used to prepare compositions including either water-soluble phenol-formaldehyde resole resins or water-soluble phenol-formaldehyde resole resins modified with a nitrogenous reactant such as urea and/or ammonia. In the case of urea-modified phenol-formaldehyde resins, the present invention provides unexpected improvement in binder cure profiles. The present process provides compositions that exhibit very good stability, even at low pH.

[0016] The process comprises preparing a water-soluble phenol-formaldehyde resole resin by first preparing an initial aqueous mixture including formaldehyde and phenol, and adding a basic polymerization catalyst to the initial aqueous mixture. The aqueous mixture is then maintained at a predetermined temperature during reaction of the phenol and formaldehyde to form the water-soluble phenol-formaldehyde resole resin until the free formaldehyde content of the aqueous mixture drops to a predefined level. Next, the aqueous mixture is cooled, and finally acidified to a pH of no greater than 3. Preferably, the aqueous mixture including the unmodified resole resin is acidified to a pH from about 2 to 3.

[0017] The acidified resole resin of the present process is stable at low pH. The acidified resole resin can be modified by subsequent addition of one or more acidic modifiers to alter or improve the properties of the resulting resin and/or the binder subsequently prepared from the resole resin. Examples of suitable acidic modifiers that can be employed include latent catalysts such as ammonium sulfate, reactive diluents such as benzylic alcohols, weak acids such as boric acid, and fatty acids such as oleic and stearic acids, polycarboxylic acids such as polyacrylic acids, and esters, such as diethyl phosphite.

[0018] Optionally, the process can be used to prepare a modified phenol-formaldehyde resin composition by preparing an aqueous reaction mixture including the phenol-formaldehyde resole resin and a nitrogenous reactant, such as urea, ammonia, or a mixture of urea and ammonia; and permitting the nitrogenous reactant to react with the phenol-formaldehyde resole resin to form a modified resin.

[0019] Subsequently, preparation of the binder is completed by adding a catalyst for curing the resole resin.

[0020] Preferably, the phenol-formaldehyde resin has a formaldehyde-to-phenol mole ratio of from about 2.5:1 to 4.2:1, and more preferably, from about 3.2:1 to 4.0:1. It is also preferred that the predefined level be about 40 percent by weight of the free formaldehyde in the initial aqueous mixture.

[0021] Further, the process of the present invention also optionally provides for adding ammonia and/or urea to the reaction mixture as a formaldehyde scavenger. Preferably, the ammonia is added in sufficient quantity to give a weight ratio of formaldehyde scavenger to solids of unmodified resin of from about 1.0:100 to 3.0:100.

[0022] When a urea or ammonia-modified binder is desired, it is preferred that the mole ratio of the urea or ammonia modifying agent to the free formaldehyde of the phenol-formaldehyde resin be from about 1:1 to 1.75:1, and that the aqueous mixture be maintained at a temperature of from about 5° C. to 30° C. while permitting the modifying agent to react with the resole resin.

[0023] The present invention also provides a process for producing a glass fiber batt, which comprises preparing a binder as described above and spraying the binder on glass fibers to form a batt; and then curing the binder at an elevated temperature.

[0024] In completing preparation of the aqueous mineral fiber binder composition, other typical binder components, such as an acid elevated temperature cure catalyst, a mineral oil lubricant, and an organo-silane adhesion promoter, can be added to the aqueous mixture of the modified resole. Such components can be added to the aqueous mixture of modified resole resin shortly before application of the binder to the glass fibers.

BRIEF DESCRIPTION OF THE DRAWINGS

[0025]FIG. 1 shows cure profiles measured by differential scanning calorimetry for example 10.

[0026]FIG. 2 shows cure profiles measured by differential scanning calorimetry for example 12.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The phenol-formaldehyde resole resin employed in the process of the present invention can be prepared by conventional methods known in the art, such as those which give water-soluble resole resin and employ commercial grade phenol and formaldehyde materials. For example, the formaldehyde can be provided in the form of an aqueous formalin solution have 30-50 percent by weight formaldehyde, although other forms of formaldehyde known to the art can also be used. In addition to phenol itself, other hydroxy-functional aromatic compounds can be employed, or used in addition to phenol. Examples of substituted phenols that can be used include alkyl-substituted phenols, such as o-cresol, m-cresol, and p-cresol, 3,5-xylenol, 3,4-xylenol, 3,4,5-trimethyl phenol, 3-ethyl phenol, 3,5-diethyl phenol, p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, and p-octyl phenol; cycloalkyl-substituted phenols such as cyclohexyl phenol and 3,5-dicyclohexyl phenol; alkenyl-substituted phenols; aryl-substituted phenols such as p-phenyl phenol; alkoxy-substituted phenols such as 3,5-dimethyoxyphenol, p-ethoxy phenol, p-butoxy phenol, and 3,4,5-trimethoxyphenol; aryloxy phenols such as p-phenoxy phenol; and halogen-substituted phenols such as p-chlorophenol as well as polycyclic phenols such as napthol, anthranol, and substituted derivatives. Similarly, dihydric phenols such as catechol, resorcinol, hydroquinone, bisphenol A and bisphenol F can be used. However, phenol itself is especially preferred. Mixtures of phenols can also be used, preferably, mixtures which include phenol itself.

[0028] Similarly, other reactive aldehydes can be substituted in whole or in part for formaldehyde to produce the aqueous solution of water-soluble resole resin. Examples of other reactive aldehydes that can be used include acetaldehyde, propionaldehyde and benzaldehyde. Formaldehyde is especially preferred.

[0029] The preparation of resole resins is reviewed and described in R. W. Martin, The Chemistry of Phenolic Resins (John Wiley & Sons, Inc., New York 1956) at 88-97.

[0030] The process of this invention relates to the preparation of a water-soluble phenol-formaldehyde resole resin. A base-catalyzed condensation of the phenol and the aldehyde is typically used to prepare the resin. The reaction, which is exothermic, is initiated after mixing the phenol and the aldehyde by addition of the catalyst. The proportion of phenol to the aldehyde is selected to yield a resole-type resin (stoichiometric excess of formaldehyde) when formaldehyde and phenol are used, the mole ratio of formaldehyde to phenol preferably being from about 2.5:1 to 4.2:1, and more preferably from about 3.2:1 to 4.0:1. Preferably, an aqueous mixture of formaldehyde and phenol is maintained at a first temperature of from about 40° C. to 50° C. as a basic polymerization catalyst is added.

[0031] The catalyst used in the process of preparing the resole resin can include at least one basic alkali metal or alkaline earth metal base. Examples of alkali metal bases that can be used include the hydroxides of sodium, potassium, and lithium. Examples of alkaline earth metal bases that can be used include the oxides and hydroxides of calcium, barium and strontium, such as calcium oxide and calcium hydroxide. Potassium hydroxide or sodium hydroxide is preferred over calcium hydroxide, as the alkali metal bases appear to provide greater stability than calcium hydroxide in the present process. Other strongly basic water-soluble substances that do not react with formaldehyde, such as tertiary amines such as triethylamine, tertiary amino alcohols such as 2-dimethylamino-2-methyl-1-propanol and 2-(dimethylamino)-2-(hydroxmethyl)-1,3-propanediol, and the like, can also be used in catalyzing the preparation of the resole resin.

[0032] The temperature is then preferably permitted to rise the first temperature to a second temperature, preferably between about 60° C. and 80° C., and more preferably 70° C. The time required for the temperature rise to occur depends on the scale on which the exothermic reaction is being carried out. On a production scale, this temperature rise can occur over a period of about thirty minutes. If desired, the reaction vessel can be cooled to slow the temperature increase.

[0033] This second temperature is preferably maintained until the free formaldehyde content of the aqueous mixture drops by about 65 percent of the initial free formaldehyde level and more preferably by about 60 percent of the initial free formaldehyde level, by weight.

[0034] Next, the aqueous mixture is preferably cooled, preferably to a temperature between about 20° C. and 30° C., and the aqueous mixture is acidified, preferably to a pH of about 3 or less, more preferably to a pH of from about 2.5 to 3.5. Unexpectedly, such resins neutralized to a pH of about 3 or less exhibit actual solids that are greater than theoretical solids (based on unneutralized solids).

[0035] The aqueous mixture is preferably acidified with a strong acid, such as a strong mineral acid. Examples of acids that can be used include mineral acids such as sulfuric acid, including 25% sulfuric acid solution, hydrochloric acid, nitric acid, and phosphoric acid and organic acids such as acetic acid, tricholoracetic acid, and aromatic di- and polysulfonic acids, including phenyl sulfonic acids, such as p-toluene sulfonic acid, and other organosulfonic acids.

[0036] Typically, the process is selected to provide an aqueous resole resin with total solids of about 40 to 50 percent by weight. The aqueous resole resin can also include small amounts of residual formaldehyde, such as up to about 15 percent by weight, and small amounts of residual phenol, such as up to about 2 percent by weight. In addition, the aqueous resole resin will typically contain small amounts of residual sodium, calcium or like salts from the resin polymerization.

[0037] Because the acidified resole resin of the present process is stable at low pH, the acidified resole resin can be modified by subsequent addition of one or more acidic modifiers to alter or improve the properties, such as the cure characteristics, of the resulting resin and/or the binder subsequently prepared from the resole resin. The amount of acidic modifier employed depends upon the nature of the modifier and the extent of modification desired. Examples of suitable acidic modifiers that can be employed include latent catalysts such as aryl phosphites, salts of a primary or secondary amine and a strong acid, partial phosphate esters; reactive diluents such as benzylic alcohols; weak acids such as boric acid, and fatty acids such as oleic and stearic acids; and polycarboxylic acids such as polyacrylic acids. Aryl phosphite latent catalysts are disclosed, for example, by U.S. Pat. No. 5,317,050, as alternatives to strong acid catalysts for rapid hardening of phenolic resins at relatively modest elevated temperatures. Amine salts of strong acids are disclosed as effective latent catalysts for phenolic resins by U.S. Pat. No. 5,243,015, which also discloses the synergistic combination of such a latent catalyst with a minor amount of conventional strong acid cure catalyst. U.S. Pat. No. 5,378,793 discloses partial phosphate esters as latent catalysts for phenolic resole resins, the partial phosphate esters being prepared by reaction of condensed phosphoric acids with polyols under controlled conditions. U.S. Pat. No. 6,133,403 discloses benzylic alcohols, namely alkoxy benzyl alcohols and dibenzyl ethers, as reactive diluents for phenolic resins hardenable with strong acid cure catalysts. The use of polyacrylic acids as an acidic modifier for resole resins is disclosed, for example, in U.S. Pat. No. 5,670,585 (reduction of ammonia emissions), U.S. Pat. No. 6,194,512 (preferential formation of trimethylol phenol) and U.S. Pat. No. 5,804,254 (flexibilizing additive).

[0038] After preparation of the aqueous resole resin has been completed, the aqueous resin can be packaged, as by drumming, and stored until needed or transferred to a transportation vehicle such as a tank wagon or rail car and shipped to another site where binder for mineral fiber articles is to be produced.

[0039] The aqueous resole resin of the present invention has good stability, as measured by its water dilutability. Preferably, the aqueous resole resin can be diluted by greater than 2000 to 1 even after two weeks storage at low temperature (5° C. or 40° F.).

[0040] The aqueous resole resin produced can be used to prepare an aqueous binder for articles formed using mineral fibers. Typically, in such articles, the mineral fibers, such as glass fibers, are initially formed into a non-woven mat. An aqueous binder including the resole resin is typically sprayed on newly formed, still hot, glass fibers in a forming chamber or like apparatus to yield a wool-like mass including the glass fibers, bound by the resin binder. The characteristics and utility of the article produced are determined to some extent by the type of mineral fiber used, the length and diameter of the fibers, the density, oxidation, and concentration of the fibers in the mat, and the like. For some applications, it may be desirable to weave the fibers or otherwise form a fabric from the fibers.

[0041] Alternatively, in one embodiment of the present invention, the aqueous resole resin can be modified at the resin-manufacturing site by post-reaction with one or more formaldehyde scavengers for reducing the free formaldehyde before the resin is packaged and shipped. Alternatively, formaldehyde scavengers can be added later, after the resole resin arrives at the site where it will be used. Typically, the resole resin is diluted with water, and a cure catalyst is added, to form an aqueous binder. The binder is applied to the fibrous material to be bound; and the resole is cured by application of heat. The binder may also contain other components, such as one or more formaldehyde scavengers.

[0042] Typically, a nitrogenous reactant such as urea is employed as a formaldehyde scavenger for phenol-formaldehyde resole resins. Other scavengers can also be used, including nitrogenous reactants such as ammonia, ammonium hydroxide, primary and secondary amines, thiourea, dicyandiamide, guanidine, aminotriazoles such as guanamine and benzoguanamine, melamine, melamine-formaldehyde resins and dicyandimine-formaldehyde resins. Other type of formaldehyde scavengers can also be employed, such as sodium sulfite, sodium cyanide, and resorcinol. Combinations of reactants can also be used, with the combination of urea and ammonia being presently preferred.

[0043] Preferably, formaldehyde scavenger is added in an amount sufficient to react with substantially all residual formaldehyde in the resole resin. When urea employed as the formaldehyde scavenger, the mole ratio of urea to the free formaldehyde in the aqueous mixture including the resole resin is preferably from about 1:1 to 1.75:1. On mixing the formaldehyde scavenger with the aqueous resole resin, an increase in the pH of the aqueous mixture is observed, such as an increase in pH to a range of 7 to 9.

[0044] In one embodiment of the present process, urea and ammonia are added directly to the aqueous resole mixture, after the aqueous mixture has been acidified, and preferably no more than about three days after the acidification of the reaction mixture. Advantageously, the urea and ammonia can be added just after the acidification. Preferably, the aqueous reaction mixture thus provided is agitated for at least a time sufficient to ensure complete mixing of the resole resin, the urea, and the ammonia, such as for at least about 30 to 60 minutes, using conventional liquid mixing equipment. If the acidified aqueous mixture including the resole is stored for a period before the nitrogenous reactants are added, it is preferred that the aqueous mixture be stored at a temperature below ambient, such as from about 40 to 55° F.

[0045] The phenolic resin prepared by process of the present invention has a storage stability of at least about two weeks at temperatures up to at least about 55° F.

[0046] The process of the present invention can further include subsequently completing preparation of the binder by adding a catalyst, such as a latent acid catalyst, for curing the resole resin.

[0047] Examples of catalysts for curing the resole resin include acid catalysts such as salts, preferably ammonium or amino salts of acids, such as ammonium sulfate, ammonium phosphate, ammonium sulfamate, ammonium carbonate, ammonium acetate, ammonium maleate, and the like. The acid catalyst can be added in an amount of from about 0.1 to 5 percent by weight based on the weight of the resole resin, or on the basis of the resole resin and urea in the case of a urea-modified resole resin. When a latent catalyst is employed as an acidic modifier of the resin, the amount of cure catalyst can be reduced, or the cure catalyst can be omitted entirely, depending on the type and amount of latent catalyst employed.

[0048] Completing preparation of the binder can also include addition of a lubricant composition, such as a mineral oil emulsion, and a material promoting adhesion of the modified resole resin to the glass fibers, such as a suitable silane. An example of an adhesion-improving silane that can be added is 3-aminopropyl triethoxysilane. Other additives such as finely divided mineral fibers, non-reactive organic resins such as Vinsol (trademark of Hercules) resin (derived from rosin), tall oil, surface active compounds such as lignosulfonate salts, thickeners and rheology control agents, dyes, color additives, water, and the like, can also be added to the aqueous binder.

[0049] Prior to application of the binder, the binder can be diluted by addition of water to provide a concentration suitable for application to the hot mineral fibers or mineral fiber web or mat. For example, water can be added to provide a total solids content of from about 1 to 80 percent by weight.

[0050] The aqueous binder can be applied directly to newly formed, still hot glass fibers, or to a mineral fiber mat or fabric, and subsequently dried and cured to form an article. The mineral fiber can be a glass fiber, and the mat can be a non-woven mat. The mineral fibers can be continuous or chopped or can take the form of a mineral fiber wool. When glass fiber is used, it can be formed by any conventional process, such as by flame or steam blowing, by centrifugal fiberizing, or the like. The shape, fiber, density, fiber lengths, fiber orientation, and like characteristics of the fiber mat depend on the application intended for the articles produced. One especially important application is thermal insulation. In this case, the fiber mats take the form of continuous rolls or batts of non-woven, randomly oriented glass fibers. A similar mat is used in the production of glass fiber batts for acoustic insulation.

[0051] When thermal and acoustic glass fiber insulation is to be produced, the newly formed, still hot glass fibers are typically sprayed in a forming chamber or hood with the aqueous binder to distribute a coating of binder over the fibers, and especially at contact points between fibers. If the hot fibers do not have sufficient heat content to drive off the water, the mat coated with the aqueous binder solution can be subsequently thermally dried to remove water. In either case, the resinous compounds including the resole and the nitrogenous reactant are cured to form an infusible binder for the mineral fiber mat.

[0052] The process of the present invention can also be used to prepare binders for other mineral fiber articles such as battery separators, printed circuit boards, and electrical insulation products as well as for processed wood products such as chipboard, particle board, plywood, and the like.

[0053] The following examples are illustrative of the processes, compositions, and articles of the present invention, and will be useful to those of ordinary skill in the art in practicing the invention. However, the invention is in no way limited by these examples. Unless otherwise indicated all percentages are given on a weight basis in the following examples.

EXAMPLES 1 AND 2

[0054] 100 parts of commercial grade phenol and 255 parts of a 50% (w/w) aqueous solution of formaldehyde are introduced into a reactor. The reactor is heated and the contents are agitated until the temperature of the mixture stabilizes at 45° C. The temperature is maintained at a first temperature of 45° C. and 10 parts of 50% sodium hydroxide (w/w) is added at a steady rate over a thirty-minute period. The temperature is then permitted to rise to a second temperature of 70° C. within thirty minutes, and this second temperature is maintained for 60 minutes. The reaction mixture is cooled. The pH of the resin is adjusted by addition of 25% sulfuric acid to give a pH of 2.7 (Example 1). The solids of the resin were measured and were found to be 42.97 percent by weight based on unneutralized solids, and the theoretical solids were calculated to be 42.66 percent, calculated on the same basis.

[0055] The process is repeated except that 25% sulfuric acid was added to give a pH of 7.2 (Comparative Example 1). The solids of the resin were measured and were found to be 40.96 percent by weight based on unneutralized solids, and the theoretical solids were calculated to be 42.79 percent, calculated on the same basis.

[0056] The process is repeated except that 25% sulfuric acid was added to give a pH of 5.1 (Example 2). The solids of the resin were measured and were found to be 41.36 percent by weight based on unneutralized solids, and the theoretical solids were calculated to be 42.73 percent, calculated on the same basis.

[0057] Examples 1 and 2 and Comparative Example 1 show that the acidification to a pH of less than 7 provides a higher actual solids (compared with theoretical) than neutralization to a pH of 7.

EXAMPLES 3-7

[0058] Example 1 was repeated, except that a different neutralizing acid was used as provided below to neutralize the resin to an acidic pH or a pH of about 7, the results being given in Table A below. TABLE A Exam- Neutralization Actual Theoretical ple Acid pH solids solids 1 25% sulfuric 2.7 42.97% 42.66% 2 25% sulfuric 5.1 41.36% 42.73% Comp 1 25% sulfuric 7.2 40.96% 42.79% 3 25% hydrochloric 3.3 42.38% 43.07% Comp 3 25% hydrochloric 7.5 41.01% 43.07% 4 25% nitric 4.9 41.54% 42.46% Comp 4 25% nitric 7.2 41.76% 42.50% 5 50% acetic 5.6 40.91% 44.39% Comp 5 50% acetic 7.2 42.67% 44.08% 6 25% phosphoric 5 40.53% 41.56% Comp 6 25% phosphoric 7.2 40.51% 42.37% 7 50% p-Tol* 4 43.47% 44.25% Comp 7 50% p-Tol* 7.2 42.42% 44.22%

EXAMPLE 8 Progress Report 1/93 §7.3

[0059] The process of Example 1 was repeated except that (a) the phenol-formaldehyde resole resin was neutralized to the pH provided in Table B below, and (b) the resulting resole resins were modified by addition of 0.8 parts ammonia and 21 parts urea, to provide a urea-modified phenol-formaldehyde resole resin. The solids and the free formaldehyde of the resins before neutralization, the solids of the resins after neutralization, the theoretical solids (based on the solids before neutralization) and the pH after modification, are shown in Table B below. The actual solids after modification are given in Table C below, as well as the theoretical solids, based on (a) solids before neutralization, (b) the theoretical solids after neutralization, and the (c) actual solids after neutralization, as well as the free formaldehyde and free phenol after modification, and the stability of the modified resin, as determined by the dilutability.

[0060] These results show that resins neutralized to a pH of 3 produce equivalent, if not greater, measured solids, compared with resins neutralized to a conventional pH of 7.6. On the other hand, free formaldehyde in the final product is slightly elevated for modified resins (0.72% vs. 0.67%) suggesting a possible shift in resin chemistry giving formaldehyde (HCHO) release resulting in higher solids at lower pH. TABLE B Free HCHO Theoretical pH Solids (before (before Neutralization solids (after Solids (after (modified neutralization) neutralization) pH neutralization) neutralization) resin) 43.06% 14.23% 3.04 41.95% 42.63% 7.59 7.6 42.96% 40.40% 8.18

[0061] TABLE C Theoretical Theoretical solids (after solids (after modification) modification) Actual based on based on Neut. Final Final Unneutr.'d solids (after actual neut. theor. neut. pH HCHO Phenol Dilut. solids neutraliz.) solids solids 3.04 0.72% 0.533% Infinite 53.49% 53.86% 54.40% 53.88% 7.6 0.67% 0.532% Infinite 53.59% 52.84% 52.61% 53.91%

EXAMPLE 9

[0062] The process of Example 1 was repeated except that (a) the urea and formaldehyde were reacted at 70° C. for 85 minutes instead of 60 minutes (b) the phenol-formaldehyde resole resins were neutralized to the pH provide in Table D below, and (c) the resulting resole resins were split into two samples, one remained unmodified, and the other sample was modified by addition of 0.8 parts ammonia and 21 parts urea, to provide a urea-modified phenol-formaldehyde resole resin. The solids and the free formaldehyde of the resins before neutralization, the solids of the resins after neutralization, and the stability of the resulting neutralized resins, as measured by the dilutability of the resins, are shown in Table E below.

[0063] These results show that resins neutralized to a pH of 3 produce equivalent, if not greater, measured solids, compared with resins neutralized to a conventional pH of 7.6, even with the longer reaction time of 85 minutes. The results also show that modified resin with an 85 minutes reaction time has somewhat lower stability (dilutability of 0 after 3 days). TABLE D Free HCHO Solids (before (before Resin Neutrali- neutralization) neutralization) type zation pH Dilutability 43.07% 13.07% unmodified 3.09 infinite modified 3.06 0 (day 3) unmodified 7.29 infinite modified 7.29 infinite

[0064] TABLE E Actual Theoretical solids solids (after (after neutralization) Actual solids Neutrali- Unneutr.'d neutrali- based on (after zation pH solids zation) unneut. Solids neutralization) 3.04 43.70% 44.43% 42.55% 53.88% 7.6 43.70% 41.36% 42.68% 53.91%

EXAMPLE 10

[0065] The process of Example 1 was repeated except that (a) the phenol-formaldehyde resole resins were neutralized to the pH provide in Table F below, and (b) the resulting resole resins were split into two samples, one remained unmodified, and the other sample was modified by addition of 0.8 parts ammonia and 21 parts urea, to provide a urea-modified phenol-formaldehyde resole resin. The resulting resins were stored at 40° F. Oven solids were measured on the day of neutralization.

[0066] After 24 hours all samples were infinitely dilutable and showed no signs of precipitation. TABLE F Neutrali- Actual Theoretical solids based Projected solids zation pH solids on unneutralized base of modified resin 9.45 44.32% 8.98 41.90% 43.90% 8.98 53.39% 55.63% 54.12% 8.0 41.00% 43.07% 8.0 52.34% 54.97% 53.18% 6.91 41.26% 43.19% 6.91 52.60% 54.85% 53.30% 4.21 40.85% 43.18% 4.21 53.16% 54.76% 52.78% 3.14 42.62% 43.14% 3.14 53.04% 54.70% 54.31%

EXAMPLE 11

[0067] A urea-modified phenol-formaldehyde resin was prepared as in Example 10 above and split into two samples, one of which was neutralized to pH of 7.6, the other of which was neutralized to a pH of 3.12. Similarly, the base resin was split and one of the samples was neutralized to a pH of 3. The percent formaldehyde, percent phenol, percent solids, pH and dilutability were measured on the date of preparation, and after storage at 40 F.

[0068] The results are provided in Table G below. TABLE G % % % HCHO Phenol solids pH Dilutability Resin 1 day Unneutralized base 14.35 9.24 Neutralized base 13.47 3.38 Modified, neutralized 0.997 0.664 52.47% 8.38 Inf. Modified, pH 3 0.950 0.696 54.22% 7.80 Inf. % % % HCHO Phenol solids pH Dilutability Dilutability Resin 1 week 4 week Unneutralized base 43.13% Neutralized base 42.16% 3.33 Inf. Light haze Modified, neutralized 0.88 52.62% 8.25 Inf. Haze, clears with dilution Modified, pH 3 0.98 54.09% 7.65 Inf. Haze, clear with dilution

EXAMPLE 12

[0069] The process of Example 10 was repeated to provide a urea-modified resin acidified to pH 3 and an unmodified resin. Binders were prepared from the resins by adding 2.2 parts by weight ammonium sulfate to the unmodified resin (no ammonium sulfate was added to the modified resin) and the tensile strength of 257-271 lbs was measured after curing at either 160° C. or 180° C., the resin having been stored for up to 2 weeks at 40° F., as reported in Table H.

[0070] The results reported in Table H show that the binder made with the pH 3 modified resin has lower tensile strength than does the binder made with the unmodified resin including the ammonium sulfate curing catalyst, but which was judged to be acceptable for product performance purposes. TABLE H Storage at 40 F. 1 day 1 week 2 weeks Cure temperature 160 C. 180 C. 160 C. 180 C. 160 C. 180 C. Resin Tensile Strength (psi) Modified, 332.7 326.2 297.7 302.3 319.0 356.8 neutralized, ammonium sulfate Modified, 257.3 271.0 260.0 256.4 214.5 271.2 pH 3, no ammonium sulfate

EXAMPLE 13

[0071] The process of Example 12 was repeated, except that 1 part ammonium sulfate was added as a cure catalyst to the binder based on the urea-modified resin acidified to pH 3, and the resins were stored for 3 weeks before measuring tensile strength. The results reported in Table I show that the addition of 1.0 part ammonium sulfate significantly increase the tensile strength to a level comparable to the control. TABLE I Storage at 40 F. 3 weeks Cure temperature 160 C. 180 C. Tensile Strength Resin (psi) Modified, neutralized, 348.5 329.8 ammonium sulfate Modified, pH 3, ammonium 324.2 334.7 sulfate

EXAMPLE 14

[0072]FIG. 1 reports the result of a differential scanning calorimetry evaluation of the cure profiles of the two binders based on urea-modified resins, one acidified to pH 3 and the other to pH 7.6. No ammonium sulfate cure catalyst was added to these binders. The DSC traces show that the binder prepared with urea-modified resin acidified to pH 3 shows surprisingly little precure and does produce a marked increase in phenol-formaldehyde exotherm compared with the binder prepared using the binder neutralized to pH 7.6.

EXAMPLE 15

[0073]FIG. 2 reports the result of a differential scanning calorimetry evaluation of the two binders based on urea-modified resins, one acidified to pH 3 and the other to pH 7.6. Two parts by weight of ammonium sulfate cure catalyst was added to these binders. The addition of ammonium sulfate dramatically alters the cure profile of the binder based on the pH 3, urea-modified resin. The magnitude of the phenol formaldehyde exotherm is significantly reduced, and the urea-formaldehyde exotherm is also affected, showing the possibility of increased precure.

[0074] Various modifications can be made in the details of the various embodiments of the processes, compositions and articles of the present invention, all within the scope and spirit of the invention and defined by the appended claims. 

1. A process for preparing a phenolic binder for glass fibers, the process comprising a) preparing a water-soluble phenol-formaldehyde resole resin by: 1) preparing an initial aqueous mixture including formaldehyde and phenol; 2) adding a basic polymerization catalyst to the initial aqueous mixture; 3) maintaining the aqueous mixture at a predetermined temperature during reaction of the phenol and formaldehyde to form the water-soluble phenol-formaldehyde resole resin until the free formaldehyde content of the aqueous mixture drops to a predefined level; 4) cooling the aqueous mixture; and 5) acidifying the aqueous mixture to a pH of no greater than 3; b) subsequently completing preparation of the binder by adding a catalyst for curing the modified resole resin.
 2. A process according to claim 1 further comprising a) preparing an aqueous reaction mixture including the phenol-formaldehyde resole resin and urea; and b) permitting the urea to react with the phenol-formaldehyde resole resin to form a modified resin.
 3. A process according to claim 1 further comprising mixing an acidic modifier with the aqueous mixture.
 4. A process according to claim 3 wherein the acidic modifier is a latent catalyst.
 5. A process according to claim 3 wherein the acidic modifier is a reactive diluent.
 6. A process according to claim 1 wherein the phenol-formaldehyde resin has a formaldehyde-to-phenol mole ratio of from about 2.5:1 to 4.2:1.
 7. A process according to claim 6 wherein the phenol-formaldehyde resin has a formaldehyde-to-phenol ratio of from about 3.2:1 to 4.0:1.
 8. A process according to claim 1 wherein the predefined level is about 40 percent by weight of the free formaldehyde in the initial aqueous mixture.
 9. A process according to claim 2 further comprising adding ammonia to the reaction mixture wherein the ammonia is added in sufficient quantity to give a weight ratio of ammonia to solids of unmodified resin of from about 1.0:100 to 3.0:100.
 10. A process according to claim 1 wherein the aqueous mixture including the unmodified resole resin is acidified to a pH from about 2 to
 3. 11. A process according to claim 2 wherein the mole ratio of the urea to the free formaldehyde of the phenol-formaldehyde resin is from about 1:1 to 1.75:1.
 12. A process according to claim 2 wherein the aqueous mixture is agitated for at least a time sufficient to ensure complete mixing.
 13. A process according to claim 2 wherein the aqueous mixture is maintained at a temperature of from about 5° C. to 30° C. while permitting the urea to react with the resole resin.
 14. A process according to claim 2 wherein completing preparation of the binder further includes adding a mineral oil lubricant and an organo-silane adhesion promoter to the aqueous mixture including the modified resole resin.
 15. An improved binder for glass fibers prepared according to the process of claim
 1. 16. A process for producing a glass fiber batt, the process comprising: a) preparing a water-soluble phenol-formaldehyde resole resin by: 1) preparing an initial aqueous mixture including formaldehyde and phenol; 2) adding a basic polymerization catalyst to the initial aqueous mixture; 3) maintaining the aqueous mixture at a predetermined temperature during reaction of the phenol and formaldehyde to form the water-soluble phenol-formaldehyde resole resin until the free formaldehyde content of the aqueous mixture drops to a predefined level; 4) cooling the aqueous mixture; and 5) acidifying the aqueous mixture to a pH of no greater than 3; b) preparing a binder for the glass fibers by subsequently adding a catalyst for curing the modified resole resin, c) spraying the binder on glass fibers to form a batt; and d) curing the binder at an elevated temperature.
 17. The process of claim 16 further comprising a) preparing an aqueous reaction mixture including the phenol-formaldehyde resole resin and urea; and b) permitting the urea to react with the phenol-formaldehyde resole resin to form a modified resin.
 18. A process according to claim 16 further comprising adding ammonia to the reaction mixture.
 19. A process according to claim 16 further comprising mixing an acidic additive with the aqueous mixture.
 20. A product prepared by the process of claim
 16. 